In a lot of systems they are the same thing - this is why the distinction is made about whether the system has both or not. In a lot of cases it's obvious whether you're dealing with a "pressure cap" or just a simple screw top cap of some kind. I wouldn't open any pressure cap when warm/hot if I could help it.
A secondary effect of opening when warm/hot is that you've equalized the pressure at this higher temperature. When the system cools to ambient it will now be under vacuum. In my experience, there can be places which do not leak coolant/steam OUT of the system but they will allow air to be sucked in. This *could* lead to air in your system and cooling problems.
I believe a lot of pressure caps are supposed to be designed to allow air in under vacuum meaning that the location of air ingestion is controlled - low resistance through the cap instead of drawing air in near the block. Again, this may not always be the design, nor may it always be working correctly. I've seen systems with hoses sucked flat when cold.
If at all possible, I would open any part of the system at temps as close to ambient as possible to be on the safe side. There a lot of different designs out there.